1. Field of the Invention
Exemplary embodiments disclosed herein related to inks and coatings and polymerizable systems therefor. Of particular interest are polymerizable di-substituted, di-activated vinyl compositions, not including cyanoacrylates, such as, but not limited to, methylene malonates, methylene β-ketoesters, methylene β-di-ketones, dialkyl disubstituted vinyl, dihaloalkyl disubstituted vinyl, whether monofunctional, difunctional or multifunctional monomers, oligomers or polymers.
2. Background
Methylene malonates are compounds having the general formula (I):
wherein R and R′ may be the same or different and may represent nearly any substituent or side-chain. Such compounds have been known since 1886 where the formation of diethyl methylene malonate was first demonstrated by W. H. Perkin, Jr. (Perkin, Ber. 19, 1053 (1886)).
However, earlier methods for producing methylene malonates suffer significant deficiencies that preclude their use in obtaining commercially viable monomers. Such deficiencies include unwanted polymerization of the monomers during synthesis, formation of undesirable side products, degradation of the product, insufficient and/or low yields, and ineffective and/or poorly functioning monomer product. These problems have impinged on their practical use in the production of commercial and industrial products.
Certain co-inventors of the instant application have recently filed patent applications on improved methods of synthesis of methylene malonates, namely, PCT/US11/056903 Synthesis of Methylene Malonates Substantially Free of Impurities, and PCT/US11/056926 Synthesis of Methylene Malonates Using Rapid Recovery in the Presence of a Heat Transfer Agent. The synthesis procedures provided therein result in improved yields of heretofore elusive high quality methylene malonates and other polymerizable compositions.
The polymerizable compositions are amenable to chain-building and/or cross-linking polymerization by anionic or free radical initiation and have the potential to form the basis of a highly valuable and large-scale platform for the chemical synthesis and formulation of new chemical products.
In the art, there exists a need for new classes of commercially viable products, in particular, inks and coatings. Specifically, the commercial reduction to practice of a low or zero energy input, very fast polymerizing addition polymer platform with far ranging property sets coupled with crosslinking that is also by design environmentally, biologically or metabolically compatible with most living organisms that is finally also either in whole or part made from a broad sustainable resource base, including sugars, atmospheric gases, waste gases and synthesis gas opens up a vast array of new technologies that can deliver great benefits to society.
One particular need in the art is for coatings, inks and the like where a protective and/or decorative layer could be applied as a 100% solids reactive composition that could cure, if desired, nearly instantaneously, with little or no energy input. Such ink or coating compositions could have dramatic impact on energy use reduction as well as significant reduction in solvent use. Either alone or in combination with a surface activator, such systems would eliminate the need for two part condensation polymerization or addition polymerization systems where complex, precise mixing and metering systems are required. Further, such systems would reduce or eliminate the need for sophisticated ovens required to control temperature and solvent volatilization. Finally, such desirable systems would reduce the level of catalyst, preferably less than 2% by weight catalyst, to dramatically reduce leaching non-bound chemical elements and provide for more facile activation.
Such a non-thermally activated and/or accelerated system dramatically would change the types of materials one could use in manufacturing the related substrates and the steps at which they could be used. By example, where certain thermoplastics or decorative elements may not survive a typical 150° C. or higher oven cure for 20 minutes or more, at ambient temperatures virtually any known material could be utilized.
In the art is it desired to provide functional and/or decorative coatings or inks that could be 100% solids and that would not require pre-polymerization into emulsions. It is also desired to have such coatings or inks that would be environmentally resistant, that did not require energy input (heat or light) for activation. Such coatings and inks could provide key benefits such as the substantial reduction of energy use on application and cure, elimination of complex solvent handling and recovery equipment, the elimination of the energy related equipment, and the ability to use said systems for thermally sensitive substrates. By example, the ability to replace ultraviolet light cure systems for inks and overprint varnishes would provide all of the aforementioned benefits. Also desired is the replacement of emulsion-based inks where environmental resistance is poor, where 50% water compositions must be contained and shipped and managed and where an instant cure would provide for far more raid throughput for the office or home user where ultraviolet light systems are costly, complex and even dangerous to manage.
Thus, new classes of commercially viable products, in particular, coating and ink formulations, processes and application equipment and the articles utilizing such materials are highly desired in the art.